Malodor counteracting compositions and method for their use

ABSTRACT

The invention relates to a malodor counteractancy or counteracting (MOC) method that resorts to the use of specific malodor counteracting (MOC) mixtures of fragrance ingredients. More particularly, the invention relates to new MOC compositions capable of neutralizing or masking in an efficient manner malodors of a large variety of such as body or animal malodors, kitchen malodors, toilet and bathroom malodors, and tobacco malodor. The novel MOC compositions of the invention contain at least one nitrile material in combination with another fragrance material and can be used in any finished consumer products such as air fresheners, kitchen or toilet/bathroom cleaning or freshening products, textile treatment products and products for application on the human skin or hair, or on animal fur, litter containers or cages.

TECHNICAL FIELD

The present invention relates to a malodor counteractancy orcounteracting (MOC) method that resorts to the use of specific malodorcounteracting (MOC) mixtures of fragrance ingredients. Moreparticularly, the invention relates to new MOC ingredients capable ofneutralizing or masking in an efficient manner malodors of a largevariety of origins and which can be encountered in the air, on textiles,bathroom or kitchen surfaces, etc. The novel MOC compositions of theinvention contain at least one material of group (I) and at least onematerial of group (II), as defined below.

The invention also relates to methods of use of the MOC compositions andingredients to counteract malodor and of any finished consumer productscontaining them, such as air fresheners, kitchen or toilet/bathroomcleaning or freshening products, textile treatment products and productsfor application on the human skin or hair, or on animal fur and skin,litter containers and cages.

PRIOR ART

The prior art richness in reports of methods to counteract and/or maskmalodors is such that a complete review of all the methods andcompositions prior reported in this context is impossible here. It isclear however that there still exists a need to continue searchingalternative ways of solving the malodor problem, as evidenced by theconstant publications in this field.

Early work by A. A. Schleppnik, described in a series of US patents,namely U.S. Pat. Nos. 4,187,251, 4,310,512 and 4,622,221 and 4,719,105,disclosed the use of a variety of cyclopentyl, cyclohexyl and phenylderivatives having a lateral chain typically comprising a carboxylicfunctional group, mostly aldehydes, ketones and more particularly esterderivatives of the indicated cyclic moiety.

Also, an early review on malodor control, situating the objectives ofresearch in this field, the general chemical solution approachespossible and the potential applications thereof, was presented by H.Hoffmann in Perfumer & Flavorist, 1986, 11, pages 1 to 7.

In more recent work published in U.S. Pat. No. 5,795,566, to D. Joulain,there were proposed deodorant compositions containing at least twoaldehydes, selected from specifically defined groups.

Useful reference can also be made to the mixtures disclosed in EP780132-A1, to International Flavors & Fragrances, formed of musky,citrus and minty type fragrance ingredients, and more particularly tomixtures of Galaxolide with mint oil and citrus terpenes. In a morerecent publication, US 2004/0156742, inventors from this same companyproposed mixtures of specific esters to counter air malodor.

C. E. Kaiser et al., in WO 00/55288, proposed a method of masking aminetype malodors via addition of materials capable of forming Schiff typebases with the amines generating the malodor, whereas J. Costa et al.,from the same company, have recently postulated in US 2004/0034789 thatmalodor coverage and/or masking should be essentially based on theprinciple that the materials used for this purpose must have a high airdiffusion coefficient. The inventors in this latter publication proposedmixtures of compounds comprising phenyl and C₅ ring moieties and havingwell defined air diffusion coefficients. In spite of the other priorknown disclosures of phenyl and cyclopentyl derivatives taught for thesame purpose, the malodor masking mixtures specifically disclosed inthis latter document are shown to counteract a variety of malodors ofdifferent origins, and one can find in this document a usefuldescription of the typical malodor compositions that are used generallyfor testing efficiency of malodor coverage and/or masking.

W. Neugebauer et al., in International patent publication WO 03/070871,addressed the problem of covering the malodor generated during soakingand hand washing of laundry and postulated the use of one or morespecific fragrance ingredients. Although one can find amongst theproposed ingredients a suggestion to combine chemicals such as damasconeand decenyl nitrile with a third component of more complex structure,there is no suggestion that the simple combination of materials as arepresently taught here would efficiently provide a MOC effect.

Still amongst the more recent patent literature in this field, one cancite the report of Thomas McGee et al., in U.S. Pat. No. 6,610,648, forexample, related to the use of low odor intensity compounds to coveroffensive odors encountered in the air and a large variety of surfaces.Column 1 of this document, in particular lines 10 to 50, expose in ageneral manner the background of this technical field and the problemthat the skilled practitioner is confronted with, and its disclosure isincluded herein by reference to help situate the technical field ofrelevance to the present invention. This document also summarizessuccinctly the types of approaches that have been used in priorsolution-providing disclosures in this field and proposes a solutionbased on particular compounds that are said to act synergetically,whilst being individually odorless or of a neutral odor.

The description above clearly shows that, although many attempts havebeen made at solving malodor masking or coverage, or the development ofmalodors in air or in a variety of surfaces, there is a constant needfor MOC compositions and methods for their use. The present inventionprovides an original and advantageous contribution to the solution ofthis problem.

DESCRIPTION OF THE INVENTION

We have now surprisingly established that mixtures of the compounds ofgroups (I) and (II) described below possess very useful MOC propertiesand that they are capable of masking and/or neutralizing a large varietyof malodors of importance in the design and conception of fragrancecompositions and consumer products intended for efficient preventionand/or masking of malodor development in the human or animal bodies, orgenerated as a result of human and animal general activities.

The present invention relates to MOC compositions comprising at leastone ingredient selected from Group (I) compounds and at least oneingredient selected from Group (II) compounds, wherein the Group (I)compounds and the Group (II) compounds are defined as follows:

A. Group (I):

-   (i) Compounds of formula

having one or two double bonds in the C₆ ring, located in the positionsindicated by the dotted lines and wherein:

-   a) R¹ represents a group of formula

-   -   R⁵ being hydrogen or a C₁ to C₄ linear or branched alkyl        radical, or an allyl radical, and R⁶ representing hydrogen or a        C₁ to C₄ linear or branched alkyl radical;

-   b) R² is H, ═CH₂ or —CH₃;

-   c) R³ is H or a C₁ to C₄ linear or branched alkyl radical; and

-   d) R⁴ is H or a C₁ to C₄ linear or branched alkyl radical;

-   the sum of carbons atoms in groups R², R³ and R⁴ being less than, or    equal to, 7; or

-   (ii) Compounds of formula

in which n is 1 or 2, R⁷ represents a C₁ to C₁₀ linear or branched alkylor allyl radical, and R⁸ is H or a C₁ to C₄ linear or branched alkylradical; or

-   (iii) A compound selected from group consisting of the compounds of    formulae

B. Group (II)—Nitriles.

Specific examples of suitable compounds of formula (I) are representedby the following structures:

all of these materials being fragrance ingredients available fromFirmenich SA, Geneva, Switzerland.

Following a preferred embodiment of the invention, the at least onecompound from Group (I) is a compound of formula (I) comprising a singledouble bond in the ring, said double bond being located in a positionalpha relative to the substituting side chain of the ring carrying thefunctional group R¹.

Following another preferred embodiment, the at least one compound fromGroup (I) is selected from the group consisting of α-methyl-ionone,undecalactone,(±)-methyl-2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate,(E)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one) andα-damascone.

In an even more preferred embodiment, the at least one compound fromGroup (I) is selected from α-methyl-ionone and α-damascone.

Preferred nitriles from Group (II) are selected from the groupconsisting of cinnamonitrile or 3-phenyl-2-propenenitrile, citronitrile,geranyl nitrile, cytronellyl nitrile, 2-propyl-1-heptanenitrile,dodecanenitrile, all of these materials being ingredients available fromFirmenich SA, and the nitrile described in U.S. Pat. No.6,180,814, or3-(2,3-dimethyl-2(3)-cyclopenten-1-yl)butanenitrile and3-(2-methyl-3-methylene-1-cyclopentyl)butanenitrile.

In an even more preferred embodiment, the at least one nitrile of Group(II) is selected from citronellyl nitrile, 2-propyl-1-heptanenitrile andthe nitrile described in U.S. Pat. No.6,180,814.

As will become apparent from the examples presented further on, we havebeen able to establish that the combinations of one compound from Group(I) with one compound from Group (II) provide a synergetic MOC effect ascompared to the MOC effect obtained by the use of either compound alone,or as compared to the theoretical MOC effect that would have beenexpected from the simple addition of the individual MOC contributions ofthese two materials when present in a wide range of relative proportionsin a mixture. These combinations can be employed advantageously forcounteracting malodor of a variety of origins, such as sweat and otherbody malodors, kitchen (cooking) and toilet (urine, faeces) malodors,gasoline, amine and sulfur type odors, the odor of tobacco smoke, animallitter malodors, etc.

By a “synergetic” effect it is understood here an effect which is notthe simple sum or addition of the MOC effect expected when the twomaterials would have been admixed in a 50:50 proportion in the mixture,or in any other relative proportion. The contribution from eachmaterial, as a function of its concentration relative to the weight ofthe selected testing malodor mixture, is first experimentallyestablished, such that, for a given concentration of each individualmaterial of Group (I) or of Group (II), a precise MOC reduction effectcan be established.

As used herein, “a malodor counteracting (MOC) composition” is to beunderstood as a mixture of ingredients as defined above and which iscapable of reducing the perception of malodor, i.e. of an odor that isunpleasant or offensive to the human nose.

According to the invention, the individual MOC materials, and theirmixtures, are shown to reduce the malodor perceived from compositionsformed either according to International standards or as indicated inthe examples further on, and which are representative of the variousodors of interest generally recognized as being unpleasant or offensiveto the human nose.

The amount of compound or compounds of Group (I) and of compound orcompounds of Group (II) in the MOC composition of the invention can varyin a wide range of values comprised between 1 and 99% by weight of eachof the two components, relative to the weight of the MOC composition.For each combination, the optimum relative concentrations can easily beestablished as indicated in the examples presented further on.

To provide the desired MOC effects to counteract malodor in the airsurrounding a user of the MOC composition, or surrounding a surface towhich one applies said composition, the latter may be used on its own orcombined with other ingredients.

According to particular embodiments, the invention also concerns the useof the MOC compositions for preparing perfuming compositions containingother ingredients added mainly for their perfuming effect, such that theperfuming compositions of the invention comprise at least two distinctcomponents, the MOC composition of the invention and a mixture offragrance ingredients of a different nature.

To prepare a perfuming composition according to the invention, the MOCcompositions may be admixed with perfuming ingredients of a differentnature, the latter providing a desired hedonic effect of a pleasantnature. The MOC composition will typically constitute from 0.1 to 50% byweight, preferably from 5 to 50% by weight and more preferably from 9 to20%, of the total weight of the perfuming composition according to theinvention. The perfuming composition may also comprise solvents andadjuvants of current use in perfumery.

Likewise, the consumer products containing the MOC compositions of theinvention, such as deodorants, air fresheners, products for thetreatment of substrates such as textiles, kitchen and toilet surfaces,are also an object of the present invention.

According to another embodiment of the invention, there is provided amethod to mask or cover malodors of the above-mentioned types, whichmethod comprises applying to spaces, in particular air in closed spacessuch as rooms and cupboards, or to any surface intended to be deodorizedor freshened, a MOC composition according to the invention, in an amountsufficient to reduce, mask, eliminate or prevent any malodor perceptionfrom said surface or closed space. As examples of surfaces the odor ofwhich can thus be improved, one can cite human skin and hair, animalskin or fur, kitchen and toilet surfaces, the surface of animal cages orlitter containers, rubbish containers surfaces, textile and laundrysurfaces, glass windows, dishes and crockery surfaces, etc.

Said perfuming co-ingredients are typically not compounds of Group (I)or of Group (II). Moreover, by “perfuming co-ingredient” it is meanthere a compound which is used in perfuming a preparation or compositionto impart a hedonic effect. In other words such a co-ingredient, must berecognized by a person skilled in the art as being able to impart ormodify in a positive or pleasant way the odor of a composition, and notjust as having an odor.

The nature and type of the perfuming co-ingredients of the MOCcomposition in the perfumes and perfuming compositions of the inventiondo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of its general knowledge and according to intended use orapplication and the desired perfuming effect. In general terms, theseperfuming co-ingredients belong to chemical classes as varied asalcohols, aldehydes, ketones, esters, ethers, acetates, nitriles,terpene hydrocarbons, nitrogenous or sulfurous heterocyclic compoundsand essential oils, and said perfuming co-ingredients can be of naturalor synthetic origin. Many of these co-ingredients are in any case listedin reference texts such as the book by S. Arctander, Perfume and FlavorChemicals, 1969, Montclair, N.J., USA, or its more recent versions, orin other works of a similar nature, as well as in the abundant patentliterature in the field of perfumery. It is also understood that saidco-ingredients may also be compounds known to release in a controlledmanner various types of perfuming compounds.

As liquid carrier for such perfuming ingredients one may cite, asnon-limiting examples, an emulsifying system, i.e. a solvent and asurfactant system, or a solvent commonly used in perfumery. A detaileddescription of the nature and type of solvents commonly used inperfumery cannot be exhaustive. However, one can cite as non-limitingexample solvents such as di-propylene glycol, diethyl phthalate,isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol orethyl citrate, which are the most commonly used.

The perfuming ingredients may also be present in a solid form,encapsulate or dispersed in solid carriers. As appropriate solidcarriers one may cite, as non-limiting examples, absorbing gums orpolymers, or yet encapsulating materials. Examples of such materials maycomprise wall-forming and plasticizing materials, such as mono, di- ortri-saccharides, natural or modified starches, hydrocolloids, cellulosederivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins,or yet the materials cited in reference texts such as H. Scherz,Hydrokolloids: Stabilisatoren, Dickungs- und Gehermittel inLebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie,Lebensmittelqualität, Behr's VerlagGmbH & Co., Hamburg, 1996. Theencapsulation is a well known process to a person skilled in the art,and may be performed, for instance, using techniques such asspray-drying, agglomeration or yet extrusion; or consists of a coatingencapsulation method, including coacervation and complex coacervationtechniques.

Furthermore, the invention's MOC compositions on their own or ascomponents of the perfuming compositions according to the invention, canalso be advantageously used in all the fields of modern perfumery topositively impart or modify the odor of a consumer product into whichthey are incorporated. Consequently, a consumer article or productcomprising the MOC or perfuming compositions according to the invention,as defined above, is another object of the present invention.

Such consumer products typically comprise a consumer product base, inaddition to the MOC and/or perfuming composition of the invention.

For the sake of clarity, by “consumer product base” we mean here a basewhich is distinct from, but compatible with, the MOC and perfumingcompositions of the invention, and which is typically formed ofsubstances capable of achieving the functional effect typically requiredfrom that product, such as cleaning, softening, freshening, deodorizingand others. Typical consumer product bases are the functional mixturesof ingredients that form the base of for example a surface or textiledetergent or soap, a surface or textile softener, an air freshener, acosmetic preparation, a deodorant, etc.

The nature and type of the constituents of the consumer product base donot warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of its general knowledge and according to the nature and thedesired effect of said product.

Examples of suitable consumer product bases include those of solid orliquid detergents and fabric softeners as well as all the other articlescommon in perfumery, namely perfumes, colognes or after-shave lotions,perfumed soaps, shower or bath salts, mousses, oils or gels, hygieneproducts or hair care products such as shampoos, body-care products,deodorants or antiperspirants, air fresheners and also cosmeticpreparations. Detergents include cleaning products for washing up or forcleaning various surfaces, e.g. intended for textile, dish orhard-surface treatment, whether they are intended for domestic orindustrial use. Other perfumed articles are fabric refreshers, ironingwaters, paper or non-woven substrates generally used for domesticcleaning of kitchen and bathroom surfaces in particular, or yet wipesand bleaches.

Some of the above-mentioned consumer product bases may represent anaggressive media for the MOC or perfuming compositions of the invention,so that it may be necessary to protect the latter from prematuredecomposition, for example by encapsulation.

The proportions in which the MOC compositions, or the perfumingcompositions containing them, can be incorporated into the variousaforementioned consumer articles or products may vary within a widerange of values. These values are dependent on the nature of the productas well as on the desired malodor counteracting effect that one wants toachieve. In many of these consumer products, the amount of perfumingcomposition containing the MOC component that is added to the consumerproduct is the typical amount that can be found currently in each typeof consumer product and can be easily adjusted by the skilled formulatoraccording to the perfuming and malodor counteracting effect that isdesired to achieve and the nature of the consumer product in question.

In the case of air fresheners for instance, the air freshenercomposition intended for diffusion into its surroundings and which isusually contained in a recipient forming the main body of the airfreshener, may be entirely formed of the perfuming compositions of theinvention, together with an appropriate solvent such as water and or anorganic solvent or may even consist of just the MOC compositionaccording to the invention, if this is desired.

The malodor counteracting compositions and perfumes intended for airfreshener use may also contain some optional ingredients acting as, forexample, solvents, thickeners, anti-oxidants, dyes, bittering agents anduv inhibitors.

The presence of one or more solvents may be useful to have asingle-phase liquid and/or to modulate the speed of evaporation of theactive material into the surrounding air. Said solvents may belong tothe families of isoparaffins, paraffins, hydrocarbons, namely glycols,glycol ethers, glycol ether esters, esters or ketones.

Examples of commercially available solvents useful to the invention areknown under the tradename Isopar® H, J, K, L, M, P or V (isoparaffins;origin: Exxon Chemical), Norpar® 12 or 15 (paraffins; origin: ExxonChemical), Exxsol® D 155/170, D 40, D 180/200, D 220/230, D 60, D 70, D80, D 100, D 110 or D 120 (dearomatised Hydrocarbons; origin: ExxonChemical), Dowanol® PM, DPM, TPM, PnB, DPnB, TPnB, PnP or DPnP (glycolethers; origin: Dow Chemical Company), Eastman® EP, EB, EEH, DM, DE, DPor DB (glycol ethers; origin: Eastman Chemical Company), Dowanol® PMA orPGDA (glycol ether esters; origin: Dow Chemical Company) or Eastman® EBacetate, Eastman® DE acetate, Eastman® DB acetate, Eastman® EEP (allglycol ether esters; all origin: Eastman Chemical Company).

Other examples of solvents useful are dipropylene glycol, propyleneglycol, ethylene glycol ethyl ether acetate, ethylene glycol diacetate,isopropyl myristate, diethyl phthalate, 2-ethylhexyl acetate, methyln-amyl ketone or di-isobutyl ketone.

Dyes are other optional ingredients of the MOC compositions forairfresheners. Suitable dyes are oil-soluble and can be found in theColour Index International, published by The Society of Dyers andColourist. Non-limiting examples of suitable dyes are derivatives of theanthraquinone, methine, azo, triarylmethane, triphenylmethane, azine,aminoketone, spirooxazine, thioxanthene, phthalocyanine, perylene,benzopyran or perinone families. Examples of such dyes which arecommercially available are known under the tradename Sandoplast® VioletRSB, Violet FBL, Green GSB, Blue 2B or Savinyl® Blue RS (allanthraquinone derivatives; origin: Clariant Huningue S. A.), Oilsol®Blue DB (anthraquinone; origin: Morton International Ltd.), Sandoplast®Yellow 3G (methine; origin: Clariant Huningue S.A.), Savinyl® ScarletRLS (azo metal complex; origin: Clariant Huningue S.A.), Oilsol® YellowSEG (monoazo; origin: Morton International Ltd.), Fat Orange® R(monoazo; origin: Hoechst AG), Fat Red® 5B (diazo; origin: Hoechst AG),Neozapon® Blue 807 (phtalocyanine; origin: BASF AG), Fluorol® GreenGolden (perylene; origin: BASF AG).

DESCRIPTION OF THE DRAWINGS

FIGS. 1 a) to d) show the % malodor reduction effectiveness of the MOCcompositions A to D of the invention, described in Examples 1 to 4,against bathroom malodors.

FIGS. 2 a) to d) show the % malodor reduction effectiveness of the MOCcompositions E to H of the invention, described in Examples 5 to 8,against tobacco malodor.

FIGS. 3 a) and b) show the % malodor reduction effectiveness of the MOCcompositions I and J of the invention, described in Examples 9 and 10,against kitchen malodor.

FIG. 4 compares the experimental and the theoretical % malodor reductionof bathroom malodor achieved by different MOC compositions comprisingdiverse proportions of each of the two components of three differentpairs of compounds from Groups 1 and 2.

FIG. 5 summarizes the results of the evaluation of the six MOCcompositions of the invention described in Example 12 against bathroommalodor and shows that the malodor counteracting activity of the MOCcompositions comprising a compound (I) having a ring double bond inposition alpha relative to the substituent group R¹ perform consistentlybetter than those comprising a compound (I) wherein the double bond inthe ring lies in position beta relative to R¹.

FIG. 6 represents the malodor counteracting activity of each Group (I)raw material compound of formula (I) used on its own against bathroommalodor, as described in Example 12.

FIGS. 7 a) and b) show the ability of a laundry product containing aperfuming composition comprising a MOC composition of the invention toreduce body malodor. The results are presented for two differentconcentrations of the MOC composition, i.e. 4.5% and 9.5% by weight,relative to the total weight of the perfuming composition.

SPECIFIC EMBODIMENTS OF THE INVENTION

The invention will now be described in further detail by way of thefollowing Examples.

Examples 1 to 10 Malodor Counteracting (MOC) Compositions and Their Useto Reduce Perception of Malodor A. Malodor Counteracting Effect ofIndividual Raw Materials—General Conditions of Evaluation

A variety of raw materials from Groups (I) and (II) according to theinvention were tested, using current sensory analysis methods, for theirability to reduce the perception of malodor of the bathroom, tobacco orkitchen type.

i) Malodor Compositions

The typical malodor compositions used in these evaluations were composedof the materials indicated hereafter:

Bathroom malodor* Ingredient % w/w Dipropylene glycol 62.82 Thioglycolicacid 21.18 n-Caproic acid 6.00 n-Methylmorpholine 6.00 4-Methylphenyl3-methylbutanoate 2.18 Skatole 0.91 2-Naphthalenethiol 0.91 Total 100.00*U.S. General Services Administration Federal Supply Service InterimSpecification, FA 200-5

Tobacco Malodor**

The tobacco malodor was prepared by extraction of cigarette's ash andsmoked stub.

The ash and smoked stub of each cigarette was collected in a glass jar.For each cigarette smoked, 10 ml of ethanol were added. The mixture wasstirred in a turbula mixer for 8 hours and then filtered. The filtratewas used as the tobacco malodor.

** Origin: Firmenich SA, Geneva, Switzerland

Kitchen malodor* Ingredient % w/w Diacetyl 3.85 Pyridine 3.85 Allylsulfide 9.23 Methyl sulfide 40.00 Heptaldehyde 3.85 Paraldehyde 1.90Propionic acid 36.92 Acetic acid, glacial 0.40 Total 100.00 *U.S.General Services Administration Federal Supply Service InterimSpecification, FA 200-3

In the following description, the test concentration of the specificmalodor sample used in each case was always selected so as to provide aperceived malodor intensity, when evaluated in Sniffin® Pens asdescribed below, that was approximately of the order of 4 to 5 units inthe scale described under (ii) below.

The three types of malodor samples that were perceived as having about4.5 malodor intensity were are as follows:

Bathroom malodor—1% in propylene glycol

Tobacco malodor—30% in propylene glycol

Kitchen malodor—0.3% in propylene glycol.

ii) Sample Preparation

Each raw material to be evaluated for MOC effect against one of themalodor compositions was diluted at 10% by weight in propylene glycol.The typical bathroom malodor sample was diluted at 2% by weight inpropylene glycol, the tobacco malodor was diluted at 60% by weight inpropylene glycol and the kitchen malodor was diluted at 0.6% by weightin propylene glycol.

3 G of each raw material solution as above and 3 g of the bathroom,tobacco or kitchen malodor solution, were then mixed together in aseparate beaker. Once fully homogenized, 4 g of the resulting rawmaterial/malodor solution were applied to a Sniffin Pen (Sniffin® Pensare commercially available from Heinrich Burghart GmbH). The SniffinPens thus obtained were left to equilibrate before the sensoryevaluation test.

iii) MOC Effect Against Bathroom Malodor

Each sensory test comprised the following samples:

-   -   2 Blind negative controls with bathroom malodor only@1%    -   Blind positive control with a given MOC raw material@5%    -   4 Blind test samples with 5% of a given test raw material and 1%        of bathroom malodor.

The samples were evaluated by a panel of at least 20 trained panelists.By “trained panelists” we mean here individuals that had previously beenscreened for olfactive acuity and were experienced in rating the perfumeintensity of air freshener products. Moreover, the panelists were prioracquainted with the malodor sample before carrying out the evaluationsof the raw material samples counteracting effect.

The samples were presented to the panelists in Sniffin Pens. EachSniffin Pen was labeled with a randomly generated 3 digit code. SniffinPens were presented to the panelist according to a Latin square designorder. These are presentation methods in which the samples are presentedin a balanced manner, each product being presented the same number oftimes in every position, and every possible pair is represented the samenumber of times (see Multivariate analysis of data in sensory science,edited by T. Naes, E. Risvik, Norwegian Food Research Institute,Oslovein, Norway, 1996, Elsevier, E.A. Hunter, Chapter 2).

After smelling the malodor reference sample first to familiarizethemselves with the malodor, the panelists were asked to rate themalodor intensity and the total odor intensity of each sample, based ona linear 1-7 scale (1=no odor-7=extremely strong odor) as shown herebelow:

The data generated from the panel's evaluations was statisticallyanalyzed in each case using variance analysis (ANOVA, α=0.05) and leastsignificance difference (LSD, α=0.05).

A typical example of the results is shown in Table 1 for bathroommalodor counteracting effect of four generic test raw materials (RM).

TABLE 1 Bathroom malodor counteracting by raw materials RM 1-4 SampleDescription Sample (w/w % of ingredients relative to Malodor OverallOdor No. total sample weight) Intensity Intensity 1 RM 1 (5%) + BathroomMalodor x₁ y₁ FA 200-5 (1%) 2 RM 2(5%) + Bathroom Malodor x₂ y₂ FA 200-5(1%) 3 RM 3(5%) + Bathroom Malodor x₃ y₃ FA 200-5 (1%) 4 RM 4(5%) +Bathroom Malodor x₄ y₄ FA 200-5 (1%) 5 Bathroom Malodor FA 200-5 (1%) x₅y₅ 6 Bathroom Malodor FA 200-5 (1%) x₆ y₆ 7 RM* (5%) x₇ y₇ *Raw materialn, n being an integer from 1 to 4

The results of the evaluation of the malodor samples 5 and 6 allow thecalculation of a malodor total odor mean value using the equation:

x _(mal)=(x ₅ +x ₆)/2.

This x_(mal) value is then used to calculate the % of malodor reduction,or malodor counterancy effect MOC, of each individual raw material RM 1to 4, according to the following equation:

% MO reduction_(n)=100*(1−(x _(n)−1)/(x _(mal)−1))

n being an integer of 1 to 4, designating the specific raw material inquestion in each evaluation test.

The above example is typical for all MOC evaluation tests carried outwith individual malodor counteracting raw materials against the threetypes of malodor samples, bathroom, tobacco and kitchen malodors.

B. Malodor Counteracting Effect of the MOC Compositions According to theInvention—General Conditions of Evaluation i) Sample Preparation

Each of the two raw materials to be admixed to provide a MOC compositionaccording to the invention was diluted at 10% by weight in propyleneglycol. The typical bathroom malodor sample was diluted at 2% by weightin propylene glycol, the tobacco malodor was diluted at 60% by weight inpropylene glycol and the kitchen malodor was diluted at 0.6% by weightin propylene glycol.

1.5 G of each of the two raw material solutions obtained were admixed toprovide the MOC composition solution which was added to 3 g of thebathroom, tobacco or kitchen malodor solution in a separate beaker. Oncefully homogenized, 4 g of the resulting MOC composition solution/malodorsolution were applied to a Sniffin Pen (Sniffin Pens are commerciallyavailable from Heinrich Burghart GmbH). The Sniffin Pens thus obtainedwere left to equilibrate before the sensory evaluation test.

ii) Effect of the MOC Compositions Against Malodor

The samples as prepared above were evaluated in a manner similar to thatdescribed under A., using the same methods, for malodor counteractingeffect against the same typical malodor samples. The results of theevaluations for a specific MOC composition thus provide a generic Table2, as follows, for each MOC composition.

TABLE 2 Bathroom malodor counteracting by MOC compositions SampleOverall Sample Description (w/w % of ingredients Malodor Odor No.relative to total sample weight) Intensity Intensity 8 MOC Composition 1(5%) + Bathroom X₈ Y₈ Malodor FA 200-5 (1%) 9 MOC Composition 2 (5%) +Bathroom X₉ Y₉ Malodor FA 200-5 (1%) 10 MOC Composition 3 (5%) +Bathroom X₁₀ Y₁₀ Malodor FA 200-5 (1%) 11 MOC Composition 4 (5%) +Bathroom X₁₁ Y₁₁ Malodor FA 200-5 (1%) 12 Bathroom Malodor FA 200-5 (1%)X₁₂ Y₁₂ 13 Bathroom Malodor FA 200-5 (1%) X₁₃ Y₁₃ 14 MOC composition*(5%) X₁₄ Y₁₄ *MOC composition n, n being an integer from 8 to 11

The results of the evaluation of the malodor samples 12 and 13 allow thecalculation of a malodor total odor mean value using the equation:

x _(mal)=(x ₁₂ +x ₁₃)/2.

This x_(mal) value is then used to calculate the % of malodor reductionof each MOC composition, according to the following equation:

% MO reduction_(n)=100*(1−(x _(n)−1)/(x _(mal)−1))

n being an integer of 8 to 11, designating the specific MOC compositionin question in each evaluation test.

A theoretical % malodor reduction value for each MOC composition,against each malodor type, is also calculated as the arithmetic averageof the % malodor reduction values obtained as in A. for the two rawmaterials that are combined in each MOC composition of the invention.

For example, if MOC composition 1 in Table 2 is a 50:50 mixture of rawmaterials RM 1 and RM 2 of Table 1, then the theoretical % malodorreduction value for MOC composition 1 against bathroom malodor is equalto (x₁+x₂)/2, x₁ and x₂ being the same values as in Table 1. If thistheoretical value is below the experimental Table 2 X₈ value obtainedwith this MOC composition 1 against bathroom malodor, then thecombination of raw materials RM 1 and RM 2 provides an unexpectedsynergic effect against bathroom malodor.

The above example is typical for all MOC compositions evaluation testscarried out against the three types of malodor samples, bathroom,tobacco and kitchen malodors.

C. MOC Compositions According to the Invention and Their Use toCounteract Malodor i) Effect Against Bathroom Malodor Examples 1 to 4

A variety of MOC compositions A to D were prepared by admixing thecorresponding raw materials indicated in Table 3, in a range of relativeproportions varying from 1:99 to 99:1 of each of the raw materialsindicated.

TABLE 3 MOC compositions and their components MOC Composition RawMaterial A* Raw Material B* A Nitrile described in Violette BC¹⁾ U.S.Pat. No. 6,180,814 B Citronellyl nitrile Koumalactone²⁾ C Citronellylnitrile γ-Methylionone D 2-Propyl-1-heptanenitrile α-Damascone¹⁾β-Ionone ²⁾perhydro-3,6-dimethyl-benzo[b]furan-2-one

FIGS. 1 a) to d) show the % malodor reduction effectiveness of the MOCcompositions A to D against bathroom malodors.

ii) Effect Against Tobacco Malodor Examples 5 to 8

A variety of MOC compositions E to H were prepared by admixing thecorresponding raw materials indicated in Table 4, in a range of relativeproportions varying from 1:99 to 99:1 of each of the raw materialsindicated.

TABLE 4 MOC compositions and their components MOC Composition RawMaterial A* Raw Material B* E Citronellyl Nitrile 1-(4,66-trimethyl-1,3-cyclohexadien-1-yl)-2- buten-1-one F Citronellyl Nitrile1-(2,66-trimethyl-1(2)- cyclohexen-1-yl)-1,6- heptadien-3-one GCitronellyl Nitrile δ-Damascone H Citronellyl Nitrile γ-Methylionone*Origin: Firmenich SA, Geneva, Switzerland

FIGS. 2 a) to d) show the % malodor reduction effectiveness of the MOCcompositions E to H against tobacco malodor.

iii) Effect Against Kitchen Malodor

Examples 9 and 10

MOC compositions I and J were prepared by admixing the corresponding rawmaterials indicated in Table 5, in a range of relative proportionsvarying from 1:99 to 99:1 of each of the raw materials indicated.

TABLE 5 MOC compositions and their components MOC Composition RawMaterial A* Raw Material B* I Citronellyl Nitrile δ-Damascone JCitronellyl Nitrile γ-Methylionone *Origin: Firmenich SA, Geneva,Switzerland

FIGS. 3 a) and b) show the % malodor reduction effectiveness of the MOCcompositions I and J against kitchen malodor.

The results presented in FIGS. 1, 2 and 3 clearly show that the MOCcompositions of the invention are surprisingly effective atcounteracting bathroom, tobacco and kitchen malodor, all thecompositions A to J having consistently performed above the theoreticaleffect that one might have expected if each pair had the effects simplyadded up once the materials were combined.

Moreover, a very large sample of other pairs of perfumery raw materialswere tested without such a result being observed. In fact in many cases,a negative influence could be seen when two such materials were combinedin a similar manner as exemplified above. This was especially the casewhen two perfumery raw materials carrying a lateral R¹ substituent groupin the formula (I) type compounds derived from a carboxylic acid, suchas a ketone or aldehyde group, were admixed amongst themselves.

Example 11

The ability of the preferred MOC compositions K to M from Table 6 belowto mask the synthetic bathroom malodor exposed above has been testedwith the compounds of Groups 1 and 2 mixed in different proportions.

TABLE 6 MOC compositions and their components MOC Composition RawMaterial A* Raw Material B* K Citronellyl nitrile Safrascenone¹⁾ LCitronellyl nitrile γ-Damascone M Citronellyl nitrile α-Damascone*Origin: Firmenich SA, Geneva, Switzerland¹⁾(E)-1-(4,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one

As in Examples 1 to 10 above, the malodor reduction observed during thesensory tests is compared to the theoretical malodor reduction that canbe expected for each different ratio. The results are shown in FIGS. 4a) to c). The theoretical curve (dotted line) is obtained by tracing astraight line between the values of malodor reduction obtainedexperimentally for each of the raw materials alone.

The samples have been prepared in the same way as for the previousexamples, except for the respective amounts of the two MOC ingredients,as represented in the figure. The sensory and statistical analyses havealso been performed as described above. These experimental results aresummarized in the graphs of FIG. 4 (continuous line).

A synergy is observed when the percentage of malodor reduction of theexperimental curve is higher than the theoretical percentage. The threegraphs of FIG. 4 show that, for each pair of compounds from Groups (I)and (II), certain proportions are particularly effective to mask thebathroom malodor.

The compositions corresponding to the latter proportions areparticularly advantageous and the invention therefore relates namely tothe following preferred compositions:

-   -   a) a MOC composition of safrascenone and citronellyl nitrile, in        relative proportions comprised between 1:99 and 70:30 w/w        respectively;    -   b) a MOC composition of γ-damascone and citronellyl nitrile, in        relative proportions comprised between 1:99 and 50:50 w/w        respectively;    -   c) a MOC composition of δ-damascone and citronellyl nitrile, in        relative proportions comprised between 1:99 and 99:1 w/w        respectively.

Example 12

Malodor Counteracting (MOC) Compositions Comprising a Compound ofFormula (I) as the Group (I) Component and Their Use to ReducePerception of Malodor

A variety of MOC compositions according to the invention were preparedby admixing a given nitrile compound as the Group (II) component with acompound of formula (I) having a double bond in position alpha or betarelative to the functional substituent R¹.

Thus, the following compounds of formula (I) were admixed with thenitriles indicated in Table 7 here below, in a relative proportion of50:50, to prepare six MOC compositions according to the invention thatpresented a particularly useful effectiveness against bathroom malodor.

TABLE 7 Compound of formula (I)* Nitrile* α-Ionone Nitrile described inU.S. Pat. No. 6,180,814 β-Ionone Nitrile described in U.S. Pat. No.6,180,814 α-Methylionone Citronellyl nitrile β-Methylionone Citronellylnitrile α-Damascone 2-Propyl-1-heptanitrile β-Damascone2-Propyl-1-heptanitrile *Origin: Firmenich SA, Geneva, Switzerland

The methods used were identical to those described in the general methodsection of Examples 1 to 10. FIG. 5 summarizes the results of theevaluation of the six MOC compositions grouped by the type of structureof the compounds (I) and shows that the malodor counteracting activityof the MOC compositions comprising a compound (I) having a ring doublebond in position alpha relative to the substituent R¹ performedconsistently better than those comprising a compound (I) wherein thedoube bond in the ring is in position beta.

When comparing with the results, represented in FIG. 6, obtained witheach corresponding raw material compound (I) used on its own and testedin identical concentration against the bathroom malodor, most of the MOCcompositions of the invention again showed an improved reduction of theperceived malodor, relative to the individual raw material of formula(I).

Example 13

Performance of a Perfuming Composition Comprising a MOC Composition ofthe Invention in Terms of Body Malodor Masking onto Washed Fabrics.

The ability of a perfuming composition according to the invention tomask body malodor, more specifically sweat malodor, was tested in alaundry product. Two different perfuming compositions, containingrespectively 4.5% and 9.5% by weight of the MOC composition relative tothe total weight of a same perfume were prepared. The formula of the MOCcomposition used is provided in Table 8 below. Each of the perfumingcompositions above was added to a laundry product base in an amount of0.4% by weigh, relative to the total weight of the laundry product, toprepare two laundry products according to the invention. The formula ofthe MOC composition used in the present example is provided in Table 8below.

TABLE 8 Formula of the MOC composition Ingredient Quantity4-undecanolide 60.61 Citronellyl nitrile 3.03 δ-damascone 1.528-methyl-α-ionone + 10-mehyl-α-ionone 22.72 Neobutenone alpha 3.03(E)-4-(2,6,6)-trimethyl-1-cyclohexen-1-yl)-3-butene-2-one 9.09 Total100.00

Eighteen swatches of polyester Lycra® were washed together with aballast so as to obtain a total wash load of 2.5 kg. The latter werewashed in a front load European washing machine at 40° C., withoutpre-wash, using 4 rinse cycles and 100 g of liquid detergent. The washedload was then line-dried during 24 hours under controlled conditions(22° C.-60% relative humidity).

Different test samples were prepared by washing the swatches with thelaundry product containing the perfuming composition comprising either4.5% or 9.5% by weight of the MOC composition. The samples were washed,dried and then sprayed with 0.33 g of the sweat malodor composition, onehour before the sensory evaluation. One negative control was prepared bywashing the swatch with the laundry product without any perfumingcomposition and by spraying it with the body malodor composition.Finally, two positive controls were prepared by washing swatches withthe laundry products containing the perfuming compositon either with4.5% or with 9.5% by weight of the MOC composition, no body malodorcomposition being applied.

The sensory analysis was performed with a panel of trained panelists.They were asked to rate the overall odor intensity, the perfumeintensity and the malodor intensity of each sample and control, on alinear 0-10 scale. The results of this sensory analysis were thenanalysed statistically. The final results are summarized in the chartsof FIGS. 7 a) and b).

FIG. 7 b) shows that a slight malodor reduction is already observed withthe perfuming composition comprising 4.5% by weight of the MOCcomposition. FIG. 7 a) shows that when the perfuming compositoncomprises a higher amount of the MOC composition of the invention (9.5%by weight), a significant reduction of the malodor is achieved.

According to the invention, there can be used any perfume composition towhich the MOC mixtures are added to provide similar effects. In thepresent example, we used a perfume having a top note with green, apple,aldehydic and pine connotations, completed by violet, rose medium notesand a sandalwood, plum, musk character as the bottom note.

1. Malodor counteracting (MOC) compositions comprising at least oneingredient selected from Group (I) compounds and at least one ingredientselected from Group (II) compounds, wherein the Group (I) compounds andthe Group (II) compounds are defined as follows: A. Group (I): (i)Compounds of formula

having one or two double bonds in the C6 ring, located in the positionsindicated by the dotted lines and wherein: a) RI represents a group offormula

R5 being hydrogen or a C1 to C4 linear or branched alkyl radical, or anallyl radical, and R6 representing hydrogen or a C1 to C4 linear orbranched alkyl radical; b) R2 is H, ═CH2 or —CH3; c) R3 is H or a C1 toC4 linear or branched alkyl radical; and d) R4 is H or a C1 to C4 linearor branched alkyl radical; the sum of carbons atoms in groups R2, R3 andR4 being less than, or equal to, 7; or (ii) Compounds of formula

in which n is 1 or 2, R7 represents a C1 to C10 linear or branched alkylor allyl radical, and R8 is H or a C1 to C4 linear or branched alkylradical; or (iii) A compound selected from group consisting of thecompounds of formulae

B. Group (II)—Nitriles.
 2. A MOC composition according to claim 1,wherein the Group (I) component is a compound of formula (I) comprisinga single double bond in the ring, said double bond being located in aposition alpha relative to the substituting side chain substituent R1carrying the functional group.
 3. A MOC composition according to claim1, wherein the at least one compound from Group (I) is selected fromα-methyl-ionone, undecalactone,(±)-methyl-2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate,(E)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one) anda-damascone.
 4. A MOC composition according to claim 1, wherein the atleast one compound from Group (I) is selected from α-methyl-ionone andα-damascone.
 5. A MOC composition according to claim 1, wherein the atleast one compound from Group (II) is selected from the group consistingof cinnamonitrile or 3-phenyl-2-propenenitrile, citronitrile, geranylnitrile, cytronellyl nitrile, 2-propyl-1-heptanenitrile,dodecanenitrile, all of these materials being ingredients available fromFirmenich S A, and the nitrile described in U.S. Pat. No. 6,180,814, or3-(2,3-dimethyl-2(3)-cyclopenten-1-yl)butanenitrile and3-(2-methyl-3-methylene-1-cyclopentyl)butanenitrile.
 6. A MOCcomposition according to claim 1, wherein the at least one nitrile ofGroup (II) is selected from the group consisting of citronellyl nitrile,2-propyl-1-heptanenitrile, and the nitrile described in U.S. Pat. No.6,180,814.
 7. A MOC composition according to claim 1, comprising oneGroup (I) ingredient and one Group (II) ingredients, their relativeproportions varying from 1:99 to 99:1 w/w.
 8. A MOC compositionaccording to claim 1, wherein the Group (I) component is safrascenone,wherein the Group (II) component is citronellyl nitrile and whereintheir relative proportions are comprised between 1:99 and 70:30 w/w,respectively.
 9. A MOC composition according to claim 1, wherein theGroup (I) component is y-damascone, wherein Group (II) component iscitronellyl nitrile and wherein their relative proportions are comprisedbetween 1:99 and 50:50 w/w, respectively.
 10. A MOC compositionaccording to claim 1, wherein the Group (I) component is δ-damascone,wherein Group (II) component is citronellyl nitrile and wherein theirrelative proportions are comprised between 1:99 and 99:1 w/w,respectively.
 11. A perfuming composition comprising a MOC compositionaccording to claim 1, together with a perfuming co-ingredient, a solventor an adjuvant of current use in perfumery.
 12. A perfuming compositionaccording to claim 11, wherein the MOC composition constitutes from 0.1to 50% by weight, preferably from 5 to 50% by weight and more preferablyfrom 9 to 20% by weight, of the total weight of the perfumingcomposition.
 13. A consumer article or product comprising a MOCcomposition according to claim 1, together with a consumer product base.14. A consumer article or product comprising a perfuming compositionaccording to claim 11, together with a consumer product base.
 15. Aconsumer product according to claim 13, in the form of a solid or liquiddetergent or fabric softener, a bleach, a perfume, a cologne orafter-shave lotion, a perfumed soap, a shower or bath salt, mousse, oilor gel, a hygiene product, a hair care product such as shampoo, spray orconditioner, a deodorant or antiperspirant, an air freshener or acosmetic preparation, a fabric refresher, an ironing water, a paper ornon-woven substrate or a wipe.
 16. A method to counteract malodors,which method comprises applying to a closed space, or to any surfaceintended to be deodorized or freshened, a MOC composition according toclaim 1, in an amount sufficient to reduce, mask, eliminate or preventany malodor perception from said closed space or surface.
 17. A methodaccording to claim 16, wherein the MOC or perfuming composition, or theconsumer product containing them, is applied to human skin and hair,animal skin or fur, kitchen and toilet surfaces, the surface of animalcages or litter containers, rubbish containers surfaces, textile andlaundry surfaces, glass windows, dishes and crockery surfaces.
 18. Amethod according to claim 16, which comprises using a body deodorant, oran air or fabric freshener.
 19. A method to counteract malodors, whichmethod comprises applying to a closed space, or to any surface intendedto be deodorized or freshened, a perfuming composition according toclaim 11 in an amount sufficient to reduce, mask, eliminate or preventany malodor perception from said closed space or surface.
 20. A methodto counteract malodors, which method comprises applying to a closedspace, or to any surface intended to be deodorized or freshened, aconsumer product according to claim 13 in an amount sufficient toreduce, mask, eliminate or prevent any malodor perception from saidclosed space or surface.